电极性质对异质结OLED光电性能的影响

采用空热蒸发技术制备了结构为ITO/N,N′-bis(naphthalen-1-yl)-N,N′-bis(phenyl)-benzidine (NPB)/tris-(8-hydroxyquinoline)-aluminum (AlQ)/Mg-Ag/Al的异质结结构有机电致发光器件(OLED),研究了ITO电极性质对OLED器件启亮电压、驱动电压、发光亮度和发光效率等光电性能的影响.实验结果表明,电极性质显著影响OLED器件性能,优化的电极性质通过改善电极与有机层之间的界面特性,从而改善器件的光学和电学性能.     

有机聚合物太阳电池电极的表面性能研究

采用多种方法对有机聚合物电池的电极进行表面处理,在测量接触角的基础上,应用几何平均法计算了电极样品的表面能和极性度,研究了处理方法对电极表面润湿性能的影响。结果表明,电极表面性能与其处理方法密切相关,等离子处理具有最小的接触角、最大的表面能和极性度,有效增强了电极表面的润湿性能,这一结果对于优化电极/活性层的界面性质,改善有机聚合物太阳电池的光伏性能具有非常重要的作用。     

MoO3作空穴注入层的绿光有机电致发光器件制备及其性能研究

用真空热蒸镀的方法制备了绿光有机电致发光器件,并对其工艺流程进行了详细的描述。器件结构为ITO/MoO3(xnm)/N,N′-diphenyl-N,N′-bis(1-naphthyl)-(1,18-biphenyl)-4,4-diamine(NPB)(40nm)/tris(8-hydroxyquinoline)aluminum(Alq3)(60nm)/LiF(1nm)/Al(150nm),其中x=0,5nm。实验中,对ITO基片进行氧等离子体表面处理,能够有效减小ITO表面的接触角。通过对器件的光电性能测试,研究了MoO3作空穴注入层对有机电致发光器件性能的影响。实验结果表明,空穴注入层MoO3的最高占据分子轨道(HOMO)能级较好的与ITO功函数匹配,降低了空穴注入势垒,提高了器件的发光亮度和效率。当外加电压小于10V时,器件的电流密度随外加电压的增加而增加,但变化不明显;当外加电压大于10V时,器件的电流密度明显增强,发光色度几乎不随驱动电压的改变而改变,色坐标稳定在(0.36,0.55)附近。     

退火处理对ITO表面特性及有机发光器件性能的影响

为了改善有机发光器件（OLEDs）的性能，在0～600℃不同温度下对ITO透明导电玻璃进行了退火处理。SEM观察到随退火温度的升高，ITO表面粗糙度增加；四探针电阻测试结果显示，在300℃以上温度退火后ITO表面电阻率有明显增加。用退火前后的ITO玻璃作为阳极制备了OLEDs，器件结构为ITO／TPD／Alq3／Al，比较器件的电流密度-电压特性曲线测试结果表明，ITO薄膜的热处理温度对OLEDs性能有显著的影响。     

氧等离子体处理对ITO薄膜表面性能的影响

利用原子力显微镜研究氧等离子体处理对ITO薄膜的微观表面形貌及表面润湿性能的影响。实验结果表明:经过氧等离子体处理,ITO薄膜的平均粗糙度和峰-谷粗糙度减小,薄膜的平整度提高;而且表面吸附力增大近一倍,表面能增大,接触角减小,使ITO薄膜表面的润湿性能和吸附性能得到改善。     

等离子体对OLED阳极进行处理的研究现状

大多数OLED都用ITO做阳极,为了提高ITO的功函数、改善ITO表面的平整度和减少C的污染,通常要在生长有机材料前对ITO表面进行处理。介绍了目前用等离子体对OLED阳极进行处理的研究现状,给出了Ar、O2、H2、N2、N2O和CF4等离子体处理ITO后对平整度、功函数、接触角和OLED特性等的影响,在他人研究基础上得出结论:用等离子体对OLED阳极进行处理其器件特性不仅与处理ITO表面的气体种类有关,也与产生等离子体的条件有关。采用正交试验方法可优化等离子体处理工艺参数,获得高性能的OLED。     

聚合物电致发光器件中用类金刚石碳膜增强电子注入

用正丁胺作碳源,采用射频辉光等离子系统制备类金刚石碳膜(DLC),沉积在聚合物发光器件中的发光层(MEH-PPV)和铝(Al)阴极间作电子注入层.制备了结构为ITO/MEH-PPV/DLC/Al的不同DLC厚度的器件,测量了器件的I-V特性、亮度及效率,研究了DLC层对器件电子注入性能影响的机制.结果表明:当DLC厚度小于1.0nm时,其器件有较ITO/MEH-PPV/Al高的启动电压和低的发光效率;当DLC厚度在1.0～5.0nm之间时,器件的性能随着DLC厚度增加而变好;当DLC厚度为5.0nm时,器件具有最低的启动电压与最高的发光效率;当DLC厚度继续增加时,器件的性能随着DLC厚度增加而变差.并对ITO/MEH-PPV/DLC/Al和ITO/MEH-PPV/LiF/Al的器件性能进行了比较研究.     

有机酸修饰ITO对OLED器件性能的影响

分别采用二氯苯氧乙酸和溴乙酸对ITO表面进行修饰,研究其对OLED器件(ITO/PVK/ FIrPic:SimCP/TPBi/LiF/Al)性能的影响.结果显示,相较于未修饰的器件,采用二氯苯氧乙酸修饰后的器件最大亮度由673.4 cd/m2提升至1 875.2 cd/m2,同时器件的启亮电压由6.2V降至5.3V.研究发现,有机酸处理能够改变ITO的表面能和功函数,一方面改变ITO和后续膜层的接触性能,影响后续膜层的成膜;另一方面也可以有效减少ITO与有机层间的势垒,提升载流子注入.这种用有机酸修饰ITO阳极的方法工艺简单,能有效降低空穴注入势垒,优化ITO和有机层的接触性能,对器件性能的提升起到一定的促进作用.     

基于CdSe/ZnS和Alq3的白光量子点LED的研究

采用CdSe/ZnS红光量子点(QD),利用旋涂和真 空蒸镀工艺制备了结构为ITO/TPD+PVK/QDs/Alq₃/LiF/Al的量 子点发光器件(QD-LED),并对器件的发光性能做了测试。研究了ITO表面处理、TPD空穴 传输层和QD发光层的厚 度对QD-LED性能的影响,并通过调整QD发光层和Alq₃电子传输层的 厚度,制备了可用于照明 的白光QD-LED。实验结果表明,ITO的表面处理可有效降低器件的开启电压,开启 电压从9V降到7V左右; TPD空穴传输层和QD发光层的厚度对器件的电流密度和发光亮度有较大的影响,而Alq₃电 子传输层和QD发光层 的合理配比可以混合出较高色温的白光。通过优化器件各参数,当TPD和PVK质量比为5∶1、QD度为1.0mg/ml和 Alq₃厚为60nm时,制备的器件在15V电压 时发光效率达到了1500c d/m²,色坐标为(0.3628,0.3796) ,显色指数为88.1。     

电容耦合氧等离子体处理ITO基片对OLED的影响

在不同条件下采用电容耦合氧等离子体处理用于有机电致发光（OLED）的ITO基片，使用接触电势法测量了基片表面功函数的改变。研究发现，氧等离子体处理可以有效地提高ITO表面的功函数。X射线光电子能谱的测量揭示了其本质：氧等离子体处理可以提高表面氧原子的含量，同时降低ITO表面锡／铟原子的比例，由此导致了ITO表面功函数的提高。高功函数的ITO可降低空穴由ITO向OLED空穴传输层中注入空穴的势垒，从而提高OLED器件的性能。进一步的基于联苯二胺衍生物NPB／8-羟基喹啉铝（Alq3）的标准器件的研究证明了这一点。研究同时发现，在相同的真空和氧压条件下，保持处理时间不变，随着射频激发功率的升高，ITO表面功函数会逐渐降低。这个功函数的降低，使得OLED器件的驱动电压升高且电流效率减小。因此使用电容耦合氧等离子体处理的ITO来制备OLED器件，需要在优化的条件下进行，以达最佳效果。在本实验系统下处理条件为射频功率100W、时间25s。     

Influence of electrode characteristics on the performance of organic light-emitting devices

Indium-tin oxide (ITO) substrates were treated by oxygen plasma for organic light-emitting devices (OLEDs). Using the ITO substrates aged for various times as hole-injecting electrodes, the double-layered OLEDs were fabricated by the vacuum sublimation technique, and the aging effect of treated ITO anodes on the performance of OLEDs was studied with respect to the electroluminescence efficiency, brightness and driving voltage. Experimental results reveal that the luminescent and electrical characteristics of the OLEDs are strongly dependent on the properties of the ITO anodes, and the ITO anodes aged for various times result in significant differences in device performance, which become worse with the increment of the aging time. The measurements of X-ray photoelectron spectroscopy (XPS) and surface energy show that carbon concentration increases, oxygen concentration reduces and surface energy decreases, and thereby the improved surface properties of ITO tend to decay, as the aging time increases. It indicates that the device performance of the OLEDs is closely related to the surface characteristics of the ITO anodes.     

Electrical and optical characteristics of polymer light-emitting devices with surface-treated indium-tin-oxide electrodes

Effects of differently surface-treated indium-tin-oxide (ITO) electrodes in poly[2-methoxy-5-(2′-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV)-based polymer light-emitting electrochemical cells (LECs) were investigated. It is found that the surface properties of ITO substrates are more effectively improved by the oxygen plasma compared with other treatments. Atomic force microscopy (AFM) measurements show that the oxygen plasma treatment reduces the roughness of the ITO surface and yields more smooth and homogeneous surface. X-ray photoelectron spectroscopy (XPS) analyses reveal that the oxygen plasma treatment increases the oxygen content and decreases the carbon content on the ITO surface. Contact angle and surface energy results indicate that the oxygen plasma treatment enhances the wettability of the ITO surface. The LECs with the oxygen plasma-treated ITO substrates exhibit the higher injection current, luminance and efficiency than that of the devices based on the ITO substrates treated in other different ways, due to the improvement of interface formation and electrical contact of the ITO electrode with the polymer blend in the LECs.     

A surface modification layer capable of tolerating substrate contamination on transparent electrodes of organic electronic devices

An organic molecule, hexaazatriphenylene hexacarbonitrile (HAT-CN), is found that it can be used not only as a hole-injecting material but also a surface modification material to clean contaminated substrate electrodes for the fabrication of organic electronic devices. As an example, HAT-CN can modify or “clean” indium-tin-oxide (ITO) anode surface in organic light-emitting diodes (OLEDs). Negative effect from ITO surface contamination on the electroluminescence performance of OLEDs can be dramatically reduced with this modification layer. As a result, the OLEDs with the same device architecture but with different ITO surface conditions, even with intentional contamination, can all exhibit substantially identical and superior electroluminescence performance. The surface modification function of this material is feasibly useful for the real fabrications of OLEDs as well as for advanced research on other organic electronic devices.     

Effects of surface treatment of ITO anode layer patterned with shadow mask technology on characteristics of organic light-emitting diodes

We investigated the effects of various surface treatments of indium tin oxide (ITO) on the electrical and optical characteristics of organic light-emitting diodes (OLEDs). A 150-nm-thick ITO anode layer was patterned directly with a shadow mask during the sputtering process without the use of a conventional photolithography patterning method. The sputtered ITO layer was subjected to thermal and oxygen plasma treatments to reduce the sheet resistance and improve surface roughness. The thermal treatment was performed for 1 h at temperatures of 250 and 380 °C, which were chosen so that the glass substrates would not deform from thermal damage. The measured sheet resistance decreased from 30.86 Ω/sq for the as-sputtered samples to 8.76 Ω/sq for the samples thermally treated at 380 °C for 1 h followed by oxygen plasma treatment. The root-mean-square surface roughness measured by atomic force microscopy considerably decreased to 3.88 nm with oxygen plasma treatment. The thermal treatment considerably decreased the sheet resistance of the ITO anode layer patterned with the shadow mask. The spike-like structures that are often formed and observed in shadow mask-patterned ITO anode layers were almost all removed by the oxygen plasma treatment. Therefore, a smooth surface for shadow mask-patterned ITO layers with low sheet resistance can be obtained by combining thermal and oxygen plasma treatments. A smooth surface and low sheet resistance improves the electrical and optical characteristics of OLEDs. The surface-treated ITO layer was used to fabricate and characterize green phosphorescent OLED devices. The typical characteristics of OLED devices based on surface-treated shadow mask-patterned ITO layers were compared with those fabricated on untreated and photolithography-patterned ITO layers to investigate the surface treatment effects. The OLED devices fabricated by thermal treatment at 380 °C for 1 h followed by oxygen plasma treatment for 180 s showed the highest luminance and current density. Furthermore, the leakage current that might be induced by the rough ITO surface was dramatically reduced to 0.112 mA/cm². Our study showed that the shadow mask-patterned ITO anode layer treated by heat and plasma and having a low sheet resistance and surface roughness yielded excellent electrical and optical properties for OLEDs compared to those based on an untreated ITO layer. The fabricated OLED devices using the surface-treated shadow mask-patterned ITO layer exhibited comparable characteristics to those obtained from a conventional photolithography-patterned ITO anode.     

有机/聚合物异质结电致发光器件的光电性能

器件结构是影响有机发光器件(OLED)性能的重要因素之一.采用8-hydroxyquinoline-aluminum(AlQ)作为发光层(EML)和电子传输层(ETL),polyvinylcarbazole (PVK)作为空穴传输层(HTL),制备了具有有机小分子/聚合物异质结结构的OLED器件,通过其电压-电流-发光亮度(V-J-B)特性测试,研究了HTL的引入及其膜厚对器件性能的影响.实验结果表明,HTL的引入有效地改善了OLED的光电性能,同时HTL膜厚对器件性能具有显著影响,当HTL膜厚为20 nm时,所制备的OLED器件具有最小的驱动电压和启亮电压、最大的发光亮度和发光效率.

Abstract：

The device construction plays an important role in improving the optoelectronic performance of organic electroluminescence devices (OLEDs). Heterojunction OLEDs with a configuration of glass/ITO/PVK/AlQ/Mg/Al were fabricated by using 8-hydroxyquinoline-aluminum (AlQ) as the emission layer (EML) and electron transport layer (ETL) and polyvinylcarbazole (PVK) as the hole transport layer (HTL). The effect of the HTL thickness on the performance of OLEDs was investigated with respect to the driving voltage, turn-on voltage, electroluminescence brightness and efficiency of the devices. Experimental results demonstrate that the optical and electrical properies of OLEDs are closely related to the HTL thickness. The device fabricated with the HTL thickness of 20 nm possesses the best photoelectric properties such as the minimum driving voltage and turn-on voltage, and the maximum electroluminescence brightness and efficiency.     

Effects of organic acids modified ITO anodes on luminescent properties and stability of OLED devices

In this paper, p-chlorophenylacetic acid and p-fluorophenylacetic acid were applied to modify the indium tin oxide (ITO) electrodes. The surface work functions of unmodified ITO, p-chlorophenylacetic acid modified ITO (Cl-ITO) and p-fluorophenylacetic acid modified ITO (F-ITO) are 5.0 eV, 5.26 eV and 5.14 eV, respectively, and the water contact angles are 7.3°, 59.1° and 46.5°, respectively. The increase of the work function makes the hole injection ability of the devices improved, which is proved by the hole transport devices. The self-assembly (SAM) layers transfer hydrophilic ITO to hydrophobic ITO, which makes ITO more compatible with the hydrophobic organic layers, making the organic film more stable during the operation. After modification, the organic light emitting diodes (OLEDs), SAM-modified ITO/NPB/Alq3/LiF/Al, with better performance and stability were fabricated. Especially, the OLED with Cl-ITO (Cl-OLED) has a maximum luminance of 22 428 cd/m² (improved by 32.9%) and a half-lifetime of 46 h. Our results suggest that employing organic acids to modify ITO surface can enhance the stability and the luminescent properties of OLED devices.     

Influence of plasma treatment of ITO surface on the growth and properties of hole transport layer and the device performance of OLEDs

Surface energy of indium tin oxide (ITO) surfaces treated by different plasmas, including argon (Ar–P), hydrogen (H₂–P), carbon tetrafluoride (CF₄–P), and oxygen (O₂–P), was measured and analyzed. The initial growth mode of hole transport layers (HTLs) was investigated by atomic force microscope observation of thermally deposited 2 nm thick N,N′-bis(1-naphthyl)-N,N′-diphenyl-1,1′-biphenyl-4,4′-diamine (NPB) on the plasma treated ITO surfaces. The results show that different plasma treatments of ITO influence the growth of HTLs in significantly different ways through the modification of surface energy, especially the polar component. The O₂–P and CF₄–P were found to be most effective in enhancing surface polarity through decontamination and increased dipoles, leading to more uniform and denser nucleation of NPB on the treated ITO surfaces. It was further found that increased density of nucleation sites resulted in a decreased driving voltage of OLEDs. Under the same fabricating conditions, a lowest driving voltage of 4.1 V was measured at a luminance of 200 cd/m² for the samples treated in CF₄–P, followed by the samples treated in O₂–P (5.6 V), Ar–P (6.4 V), as-clean (7.0 V) and H₂–P (7.2 V) plasma, respectively. The mechanisms behind the improved performance were proposed and discussed.